Water-soluble epoxy resins and process for their preparation

ABSTRACT

This invention is concerned with water-soluble epoxy resins represented by the general formula ##STR1## wherein A and B are independently selected from the group consisting of hydrogen and the ##STR2## radical; X is a halogen having an atomic number from 17 to 53 inclusive and a, b and c are integers the sum of which equals a number from 0 to 3. These water-soluble glycidyl ethers of glycerine are prepared by reacting glycerine with an epoxyalkyl halide in the presence of a Lewis Acid catalyst, subsequently at least partially dehydrohalogenating the resulting product, and finally recovering the water-soluble glycidyl ether product. Both the condensation reaction and the dehydrohalogenation reaction are carried out in the presence of an organic solvent. The products of this invention are polymerizable and useful in the same way as other glycidyl ethers but additionally may be used in aqueous formulations for coatings, adhesives and the like.

This application is a continuation-in-part of our copending applicationSer. No. 895,168, filed Apr. 11, 1978, now abandoned, which is adivision of our co-pending application Ser. No. 401,915 filed Sept. 28,1973, now U.S. Pat. No. 4,110,354, issued Aug. 29, 1978, which is acontinuation-in-part of our co-pending application Ser. No. 67,234,filed Aug. 26, 1970, and now abandoned, which is a continuation-in-partof application Ser. No. 852,061, filed Aug. 21, 1969, now abandoned,which is a continuation-in part of application Ser. No. 782,611, filedDec. 10, 1968, and now abandoned.

This invention relates to novel epoxy resins which are water-solubleglycidyl ethers of glycerine and to a process for the production of suchwater-soluble glycidyl ethers. More particularly, this invention relatesto a novel method for conducting the reaction of glycerine with anepoxyalkyl halide to produce chlorohydrin ether which is thendehydrohalogenated to produce a glycidyl ether of glycerine which ishighly water soluble.

The reaction of epoxyalkyl halides, such as epichlorohydrin, with apolyhydric alcohol in the presence of catalysts such as H₂ SO₄ or BF₃,is well known in the art. It is likewise well known to dehydrohalogenatethe resulting chlorohydrin ether with a base to produce a glycidylether. Such reactions, however, are normally conducted in the absence ofany solvent other than an excess of one of the reactants and the processproduces glycidyl ethers which are substantially insoluble in water.

It is an object of this invention to produce specific glycidyl ethers ofglycerine which are soluble in water. A further object is to provide tothe art a method for preparing such water-soluble glycidyl ethers ofglycerine. These and other objects and advantages of the presentinvention will become apparent from a reading of the following detailedspecification.

FIG. 1 is a graphical representation of the portion of the data ofExample 1 showing percent organic chloride plotted versus percentinsolubles.

FIG. 2 is a graphical representation of the portion of data of Example 2showing percent insolubles versus percent of product having the sum ofa, b and c in the product formula equal a number greater than 1.

It has now been discovered that water-soluble glycidyl ethers ofglycerine are prepared by reacting an epoxyalkyl halide with glycerinein a solvent and employing a Lewis Acid as a catalyst for suchcondensation reaction. The resulting chlorohydrin ether is then at leastpartially dehydrohalogenated with a base or alkaline-acting material inthe presence of a solvent to produce the desired water-soluble glycidylethers of glycerine. Such glycidyl ethers may then be separated from thesalt by filtration or centrifugation and separated from the solvent andwater by distillation.

The water-soluble glycidyl ethers of glycerine produced by the processof this invention are represented by the formula ##STR3## wherein A andB are independently selected from the groups consisting of hydrogen andthe ##STR4## radical, X is a halogen having an atomic number from 17 to53 inclusive and a, b and c are integers the sum of which equals anumber from 0 to 3. It is understood that such product is a mixture ofvarious possible species contemplated by the formula rather than being apure compound.

The term "epoxyalkyl halide" as used herein, refers to a compoundcomprising an alkane chain or cycloalkane ring having disposed thereon avicinal epoxy group (oxirane group) and a halogen atom attached to achain carbon atom which is not attached to the oxygen atom. Preferredcompounds are those wherein the halogen atom is attached to a chaincarbon atom which is directly attached to a carbon atom of an epoxyring, the vic-epoxy ring thus being in the alpha, beta-position relativeto the halogen. These compounds have the structure ##STR5## where X is ahalogen atom and each R is selected from the group consisting of thehydrogen atom and alkyl groups of up to 4 carbon atoms. Representativecompounds include 1-chloro-2,3-epoxypropane (epichlorohydrin;1-bromo-2,3-epoxypropane (epibromohydrin): 1-iodo-2,3-epoxypropane(epiodohydrin); 1-chloro-2,3-epoxybutane; 1-iodo-2,3-epoxyhexane;3-chloro-4,5-epoxyoctane; 1-chloro-2,3-epoxycyclohexane;1-bromo-2,3-epoxy-3-methylbutane; 2-chloro-2-methyl-3,4-epoxypentane;and the like, preferably having from 3 to 8 carbon atoms per molecule.The most preferred compounds of this class, which combine a terminalhalogen atom with a terminal epoxy group, are the epihalohydrins, e.g.epichlorohydrin and epibromohydrin. Because of the preponderantcommercial importance of epichlorohydrin, relative to other epoxy-alkylhalides, the following description of the invention will be made largelyin terms of that compound.

As used herein, the term "water-soluble" refers to glycidyl ethers ofglycerine containing less than 2% by volume of insolubles as determinedby the following method: 10 gm of resin (9 ml.) is admixed with water toform a total volume of 100 ml. The mixture is then shaken until no moreresin is apparently going into solution. This aqueous mixture orsolution is then centrifuged to remove any material which is not insolution. The volume of such undissolved material divided by theoriginal 9 ml. sample volume×100 provides the percent insolublescontained in the product.

Suitable catalysts for the condensation reaction between the epoxyalkylhalide and glycerine include substantially any Lewis Acid but borontrifluoride (as the etherate), aqueous hydrofluoric acid and stannicchloride have been found to be particularly effective and are thereforeusually preferred. Such catalysts are preferably employed in aproportion of about 0.01 equivalents of catalyst per glycerine hydroxygroup.

It is necessary for the purposes of this invention to react theepoxyalkyl halide with glycerine in the presence of a non-aqueoussolvent in which the glycerine is at least partially soluble and inwhich the resulting chlorohydrin ether reaction product is sufficientlysoluble to form a single phase. Suitable solvents for this reaction stepinclude ethylene dichloride (EDC), dioxane, tetrahydrofuran, ethylether, 2-chloroethyl ether, chloroform, methylene chloride and the like.It is usually desirable to employ the reactants in a solvent solutioncontaining at least about 20 weight percent solvent based on theglycerine employed with at least 50 weight percent being usuallypreferred. If less than 20 weight percent solvent is employed,undesirable amounts of water-insoluble material are formed as theproduct of this process. The upper proportion of solvent to be employedis limited only by handling and economics considerations but noparticular advantage is gained by employing over 90 weight percentsolvent. When SnCl₄ or HF rather than BF₃ or other Lewis Acid areemployed as the catalyst for this condensation step, less than 20 weightpercent solvent may be employed and in some instances no solvent isrequired in order to achieve a water-soluble product. Even with thiscatalyst, however, a solvent concentration of 50 weight percent or aboveis preferred.

Mole ratios of epoxyalkyl halide to glycerine of from about 2:1 to about2.6:1 are generally necessary to provide a water-soluble product whichis curable into a resin having desirable physical properties. When SnCl₄or HF is employed as catalysts, the mole ratio can be extended up toabout 3.0:1.

A mole ratio of substantially less than 2:1 tends to produce very lowmolecular weight products having a relatively high proportion ofmonofunctional constituents, whereas a mole ratio of substantially above2.6:1 or 3.0:1 when the catalyst is SnCl₄ or HF produces relatively highmolecular weight products having an undesirably high proportion ofmolecular species wherein the sum of a, b and c, as defined above, aregreater than 1 and which lack the desired water-solubility. Likewise,mole ratios substantially above 2.6:1 produce products having greaterthan about 8 percent organic chloride and which are therefore notsufficiently water-soluble. Therefore, the water-soluble epoxy resins ofthe present invention have an organic chloride content of from about 1.5to about 8.

A reaction temperature of between about 0° C. and the boiling point orreflux temperature of the solvent is employed in this reaction step buta temperature between about 40° C. and about 90° C. is usuallypreferred.

Alkaline-acting materials are employed to dehydrohalogenate thechlorohydrin ether to produce the desired glycidyl ethers of glycerine.Suitable alkaline-acting materials include, for example, sodiumhydroxide, potassium hydroxide, sodium and potassium carbonates and thecorresponding bicarbonates, the hydroxides of magnesium, zinc, lead,iron, aluminum and the like as well as aluminates, silicates andzincates of alkali metals. Due to its availability and price sodiumhydroxide is usually preferred and is most advantageously employed in aproportion of from about 70 to about 95 mole percent of theepichlorohydrin added. Amounts of NaOH less than about 70 percentproduce a product having a high hydrolyzable chloride content andtherefore a product having an undesirably lower epoxide content. Amountsof NaOH greater than 95% of theoretical produce higher molecular weightresins by crosslinking and such resins have insufficient watersolubility. It has been found that glycidyl ethers of glycerine having apercent organic chloride of greater than about 8 wt. percent and thosecontaining greater than about 35 wt. percent of materials having a sumof a, b and c (as above defined) which is greater than 1 are notsufficiently water soluble.

It is necessary for the process of this invention to conduct thedehydrohalogenation reaction in the presence of an organic solvent whichwill maintain at least the glycidyl ether of glycerine in solution.Suitable solvents for this step of the reaction include toluene, xylene,ethylene dichloride, methylene chloride, chloroform, and the like. It isparticularly advantageous to conduct the dehydrohalogenation at atemperature below about 110° C. and to employ a solvent which willazeotrope with water to form an azeotrope containing relatively highconcentrations of water. Under reduced pressure, solvents such astoluene and xylene are effective and for atmospheric pressuredistillation ethylene dichloride is particularly effective. While onesolvent may be employed in the condensation step, removed and a secondsolvent employed in the dehydrohalogenation step, it is usuallydesirable to employ the same solvent in both such steps.

It is important to maintain a solvent concentration in thedehydrohalogenation step of at least about 50 weight percent, preferablybetween about 70 weight percent and 95 weight percent, based on theinitial weight of glycerine plus the total quantity of solvent to beemployed in the dehydrohalogenation reaction. For example, if 80 partsof glycerine and 20 parts of solvent are employed in the couplingreaction, the addition of 167 parts of additional solvent to thereaction mixture prior to the dehydrohalogenation reaction provides asolvent concentration at the preferred 70% level based upon the weightof glycerine initially employed plus the total weight of solventemployed in the dehydrohalogenation reaction. At solvent concentrationsbelow about 50 percent relatively high percentages of water-insolublehigh molecular weight resins are formed and gelling of the resin tendsto occur. To a lesser degree such problems persist between 50 and 70percent solvent with some resin solvent systems. Above about 95 weightpercent solvent, a water-soluble resin is produced but such high volumesof solvent make recovery of the resin unduly complicated and expensive.

In one preferred embodiment of the invention, a mixture of glycerine and0.03 mole of BF₃ etherate per mole of glycerine are slurried in ethylenedichloride to form a solution containing 80 weight percent ethylenedichloride based on the glycerine present. The solution is heated to55°-60° C. and 2.5 moles of epichlorohydrin are added per mole ofglycerine at a rate sufficient to maintain the temperature within the55°-60° C. range. After the addition of epichlorohydrin, it is desirableto digest the reactant mixture for a period of time e.g. 30 minutes.After digestion, the solution is heated to a temperature of 84°-86° C.(reflux temperature) and from 0.7 to 0.95 equivalents of 50 percent NaOHper equivalent of epichlorohydrin is added to the solution. As the NaOHis added, a water-EDC azeotrope distills from the reactor. The water iscontinuously separated therefrom and the EDC returned to the reactionzone until no more water is collected. The reaction mixture is thencooled, the salt is removed by filtration or centrifugation and theresin product is recovered by flashing off the EDC solvent.Alternatively, the salt may be removed continuously during thedehydrohalogenation reaction by passing a side stream of thesolvent-product-salt slurry from the reaction vessel through a filterand returning the solvent-product filtrate to the reaction vessel. Thistechnique is particularly advantageous when the dehydrohalogenationreaction is conducted in the presence of solvent in the lower range.

For some uses, such as in coatings, adhesives and the like, it would bedesirable to prepare water-soluble glycidyl ethers of glycerine havinghigher molecular weights since such higher molecular weight resins tendto produce coatings which exhibit greater toughness, flexibility andadhesion to substrate materials than coatings prepared fromcorresponding resins which are lower in molecular weight.

Such higher molecular weight water-soluble glycidyl ethers of glycerineare prepared by the process of this invention by replacing a portion ofthe epoxyalkyl halide with a previously prepared glycidyl ether ofglycerine (hereinafter referred to as "glycidyl ether of glycerineadditive"). Such glycidyl ether of glycerine additive reacts in the samemanner as the epoxyalkyl halide but adds to the product chain a highermolecular weight unit.

In general, a mixture of an epoxyalkyl halide and a glycidyl ether ofglycerine additive comprising from about 0.05 to about 0.65 epoxideequivalents of a glycidyl ether of glycerine additive (actually amixture of glycidyl ethers of glycerine) and from about 1.35 to about2.95 epoxide equivalents per mole of glycerine of an epoxyalkyl halideis added to the glycerine and the reaction conducted as hereinbeforedescribed for the preparation of water-soluble glycidyl ethers ofglycerine.

High molecular weight water-soluble glycidyl ethers of glycerine mayalso be prepared by replacing a portion of the epoxyalkyl halide with adiglycidyl ether of a polyoxyalkylene glycol having a molecular weightof from about 200 to about 600 in proportions of from about 0.05 toabout 0.65 epoxide equivalents of the diglycidyl polyoxyalkylene glycoland from about 1.35 to about 2.95 epoxide equivalents per mole ofglycerine or an epoxy alkyl halide and conducting the reaction as abovedescribed when employing the glycidyl ether of glycerine additive.Suitable diglycidyl ethers of polyoxyalkylene glycols include thediglycidyl ethers of polyoxylpropylene glycols, diglycidyl ethers ofpolyoxyethylene glycols and the like.

The glycidyl ether of glycerine additive and diglycidyl ether of apolyoxyalkylene glycol as previously described which may be employed inthe preparation of higher molecular weight water-soluble glycidyl ethersof glycerine include any of the water-soluble glycidyl ethers ofglycerine as hereinbefore described and those glycidyl ethers ofglycerine and diglycidyl ethers of a polyoxyalkylene glycol having awater-insolubility as determined by the procedure hereinbefore describedof less than about 67 percent and preferably less than about 10 percent.

The combined epoxide equivalents of the mixture of an epoxyalkyl halideand the glycidyl ether of glycerine additive or the diglycidyl ether ofa polyoxyalkylene glycol employed is preferably from about 2.0 to about2.6. epoxide equivalents per mole of glycerine. When SnCl₄ or HF isemployed as the catalyst, the quantity can be extended to about 3.0combined equivalents per mole of glycerine. When the combined expoxideequivalent weights exceed about 2.6 or 3.0, the higher molecular weightglycidyl ethers of glycerine product obtained contains water insolubleconstituents which exceed about 2 percent by volume and when thecombined epoxide equivalent weights are less than about 2.0, the producttends to have relatively high proportions of monofunctionalconstituents.

If still higher molecular weight water-soluble glycidyl ethers ofglycerine are desired, the glycidyl ether of glycerine additive may beone which was previously prepared by reacting glycerine with a mixtureof an epoxyalkyl halide and a glycidyl ether of glycerine additive.

The glycidyl ether of glycerine additive and the diglycidyl ethers of a200-600 molecular weight polyoxyalkylene glycol are members of a classof epoxy resins which are glycidyl ethers of a compound containing morethan one aliphatic hydroxyl group.

Another method of preparing high molecular weight water-soluble glycidylethers of glycerine is to employ as the starting material in the placeof glycerine, a mixture containing (A) from about 10% to about 75%,preferably from about 10% to about 50% by weight of apolyhydroxyl-containing compound and (B) from about 90% to about 25%,preferably 90% to about 50% by weight of glycerine. When such a mixtureis employed, the other ocmponents employed are based upon the combinednumber of moles of the individual components of the mixture, e.g. thenumber of moles of epoxyalkyl halide employed would be from about 2.0 toabout 3.0 moles where the catalyst is SnCl₄ or HF and from about 2.0 toabout 2.6 when the catalyst is other than SnCl₄ or HF of an epoxyalkylhalide per the combined number of moles of glycerine and thepolyhydroxyl-containing compound.

Suitable polyhydroxyl-containing compounds include polyoxyalkyleneglycols, polyglycerols and the like.

Suitable polyoxyalkylene glycols which may be employed are thepolyoxyalkylene glycols wherein the alkylene portion contains from about2 to about 4 carbon atoms and includes, for example, polyoxyethyleneglycols, polyoxypropylene glycols and polyoxybutylene glycols, suchglycols being represented by the formula ##STR6## wherein R is hydrogen,methyl or ethyl and n is a number such that the molecular weight of thepolyoxyalkylene-glycol is from about 200 to about 600.

It is also within the scope of the present invention to prepare watersoluble glycidyl ethers which are the dehydrohalogenated reactionproducts of a mixture comprising glycerine and a polyhydroxyl-containingcompound, as previously described, with a mixture comprising anepihalohydrin and a diglycidyl ether of a polyoxyalkylene glycol aspreviously described, a glycidyl ether of glycerine additive aspreviously described, or mixtures thereof.

The following specific and comparative examples are provided to morefully illustrate the invention but are not to be construed as limitingto the scope of such invention.

EXAMPLE 1

A reaction vessel was employed which was fitted with a temperatureindicator, a stirrer and a condenser attached to a separating device forthe aqueous and organic layers. Into such flask was added 184.2 gm.glycerine, 736 gm. ethylene dichloride and 8.52 gm. BF₃ etherate. Afterheating such mixture to 55°-60° C., epichlorohydrin was added over aperiod of between about 15 minutes and 6 hours while maintaining the55°-60° C. temperature. After the epichlorohydrin addition was complete,the solution was digested at 60° C. for 30 minutes after which thetemperature was increased to 83° C.-86° C. and a quantity of 50 weightpercent aqueous NaOh was slowly added thereto over a period of from 30minutes to 8 hours while maintaining the temperature. During the NaOHaddition, water was continuously removed from the reaction vessel as anazeotrope with EDC. The water was separated from the condensed azeotropeand the solvent returned to the reaction vessel. Heating anddistillation continued for about 15 minutes until no more waterdistilled from the reaction mixture. The reaction mixture was thenallowed to cool, the salt was removed by filtration, and the product wasrecovered by flashing the EDC solvent therefrom.

Analysis of the product was then made for percent epoxide, percenthydrolyzable chloride, percent OH and percent total chloride by standardanalytical methods and percent insolubles was determined by mixing 10gm. (9 ml) of product with sufficient water to produce a total volume of100 ml, shaking the mixture for about 1 minute and centrifuging toremove the water-insolubles therefrom. The volume of such insolubles wasthen calculated as a percent by volume of the original sample.

The following table of experiments illustrates the effect of organicchloride concentration on water solubility:

                                      TABLE I                                     __________________________________________________________________________                  Caustic          %                                                            % of             Hydroly-                                                                           %    %    %                               Experiment                                                                          Epi/Glycerine                                                                         Theoretical                                                                         %     %    zable                                                                              Total                                                                              Organic                                                                            Total                           Number                                                                              Mole Ratio                                                                            (1)   Insolubles                                                                          Epoxide                                                                            Chloride                                                                           Chloride                                                                           Chloride                                                                           OH                              __________________________________________________________________________    1     2.0/1   87.5  0.0   30.9 0.0  1.9* 1.9  8.4*                            2     2.3/1   72.5  0.0   28.4 2.89 5.2* 2.31 8.4*                            3     2.25/1  75.0  0.0   28.7 1.78 6.9* 5.12 8.7*                            4     2.6/1   87.5  0.0   32.2 0.0439                                                                             7.1* 7.0561                                                                             5.3*                            5     2.6/1   85.0  0.1   30.3 0.0495                                                                             8.1* 8.0505                                                                             4.8*                            6     3.0/1   85.0   4.45 31.8 0.025                                                                              9.7* 8.675                                                                              4.1*                            7     3.0/1   70.0   5.67 30.0 1.94 11.4*                                                                              9.46 5.1*                            8     3.0/1   85.0  7.8   31.8 0.028                                                                              9.5* 9.472                                                                              3.8*                            9     3.0/1   66.0  8.9   26.6 3.25 12.3*                                                                              9.05 5.9*                            __________________________________________________________________________     *Analysis run by infrared  other determinations were by standard wet          method.                                                                       (1) Theory caustic is calculated as an equivalent of caustic per              equivalent of epichlorohydrin added to the glycerine.                    

FIG. 1 graphically demonstrates the effect of organic chlorideconcentration in the final resin. This figure was obtained by plotting %total organic chloride (% total chloride--% hydrolyzable chloride)against the % insolubles of the final product of the experiments shownin Table I.

EXAMPLE 2

In the same manner as Example 1, glycidyl ethers of glycerine wereprepared having various molecular weight distributions to demonstratethe effect of various proportions of various molecular species withinthe polymer on water-solubility. The following Table II shows thespecific reaction conditions, the molecular distribution of the polymersas determined by gel permeation chromatography and the water-solubilityof such products. The results are likewise plotted and shown graphicallyin FIG. 2.

The distribution of various species within the product mixture isdetermined by gel permeation chromatography (GPC) and therefore,referring to the product formula defined herein, the last productcomponent GPC peak represents a product wherein the sum of a, b and cequals 0, the next to last product component peak represents a productcomponent wherein the sum of a, b and c equals 1, the third to last suchpeak represents a product component wherein the sum of a, b and c equals2, and so forth. Usually, however, the first peak or two which representhigher molecular weight material (i.e. a+b+c=greater than 2) are verysmall peaks representing very small amounts of such higher molecularweight components. Analyses of the samples shown in Table II by vaporphase chromatography showed such samples to contain no free glycerineand therefore the product as analyzed by GPC contains only species whichfall within the product definition.

Since the samples analyzed by GPC in this example are prepared from thesame reactants and are therefore structurally similar, the relation ofpeak height to area is substantially constant. Therefore, for purposesof this Example the percent of products falling within a given peak orpeaks is determined by dividing the height of such peak (or sum ofheights of two or more peaks) by the sum of all the peak heights times100.

                                      TABLE II                                    __________________________________________________________________________    Epi/    Caustic     %               Peak Height in mm                             Gly-                                                                              % of        Hydro-                                                                            %   % Or-   Last Third                                                                              Second                                                                             First                                                                              % of                  Exper-                                                                            cerine                                                                            Theor-                                                                            %   %   lyzable                                                                           Total                                                                             ganic                                                                             %   Peak Peak Peak Peak Product               iment                                                                             Mole                                                                              etical                                                                            Insol-                                                                            Epox-                                                                             Chlor-                                                                            Chlor-                                                                            Chlor-                                                                            Total                                                                             (a+b+                                                                              (a+b (a+b+c                                                                             (a+b+c                                                                             Having                No. Ratio                                                                             (1) ubles                                                                             ide ide ide ide OH  C=0) +c=1)                                                                              =2)  =>2  a+b+c=>1              __________________________________________________________________________    1   2.25/1                                                                            87.5                                                                              0.0 32.8                                                                              0.008                                                                             7.1 7.092                                                                             7.3 130  115  51   26   23.9                  2   2.5/1                                                                             85.0                                                                              0.0 30.2                                                                              0.184                                                                             6.6 6.416                                                                             7.0 113  123  59   33   28.0                  3   2.5/1                                                                             87.5                                                                              0.0 32.4                                                                              0.0035                                                                            7.9 7.8965                                                                            6.0 122  128  66   34   28.6                  4   2.5/1                                                                             85.0                                                                              0.0 30.4                                                                              0.145                                                                             8.1 7.955                                                                             7.4 110  125  65   34   29.6                  5   2.3/1                                                                             72.5                                                                              0.0 28.4                                                                              2.89                                                                              5.2*                                                                              2.31                                                                              8.4 106  105  69   38   33.6                  6   2.6/1                                                                             85.0                                                                               0.10                                                                             30.3                                                                              0.0495                                                                            8.1*                                                                              8.0505                                                                            4.8*                                                                               85  105  60   34   33.1                  7   2.5/1                                                                             85.0                                                                               0.78                                                                             30.9                                                                              0.14                                                                              9.0 8.86                                                                              2.3  92  145  84   38   33.9                  8   3.0/1                                                                             85.0                                                                              7.8 31.8                                                                              0.028                                                                             9.5*                                                                              9.472                                                                             3.8*                                                                               85  116  78   42   37.4                  __________________________________________________________________________     *Analysis run by infrared  other determinations were by standard wet          method.                                                                       (1) Theory caustic is calculated as an equivalent of caustic per              equivalent of epichlorohydrin added to the glycerine.                    

EXAMPLE 3

In the same manner as Example 1, a number of experiments were conductedand tabulated to show the effects of solvent type and concentration,catalyst, and mole ratio of reactants as well as to provide a directcomparison with the water-solubility of a typical commercial glycidylether of glycerine. The indicated catalyst was employed in a quantitycorresponding to 0.01 equivalent of catalyst per glycerine OHequivalent. The results of such experiments are shown in the followingTable III.

                                      TABLE III                                   __________________________________________________________________________    Epichlorohydrin - Glycerine Reaction                                                              Dehydrohalogenation                                           Epi-Gly-                                                                           Solvent-   Solvent                                                                             Caustic      Hydro-                                 Exper-                                                                            cerine                                                                             Wt.%       Wt.%  % of Insolu-                                                                           Epox-                                                                             lyzable                                                                           Total                                                                             Organic                                                                            Total                     iment                                                                             Mole Based on   Based on                                                                            Theoret-                                                                           bles                                                                              ide Chlor-                                                                            Chlor-                                                                            Chlor-                                                                             OH                        No. Ratio                                                                              Glycerine                                                                           Catalyst                                                                           Glycerine                                                                           ical (1)                                                                           %   %   ide %                                                                             ide %                                                                             ide %                                                                              %                         __________________________________________________________________________    1   (Control) A typical, commercially available glycidyl                          ether of glycerine having an eq. wt. of 150-170.                                                         23.3                                                                              26.0                                                                              1.03                                                                              13.8                                                                              11.17                                                                              4.2                        2* 2.5/1                                                                              none  BF.sub.3                                                                           Toluene                                                                       90%   85.0 11.1                                                                              30.5                                                                              0.16                                                                              11.4                                                                              11.24                                                                              3.9                       3   2.5/1                                                                              EDC-80%                                                                             BF.sub.3                                                                           EDC-80%                                                                             85.0 0.00                                                                              30.2                                                                              0.184                                                                             6.6 6.42 7.0                       4   2.5/1                                                                              None  SnCl.sub.4                                                                         EDC-80%                                                                             85.0 1.1 30.5                                                                              0.592                                                                             5.6 5.01 4.3                       5   2.6/1                                                                              EDC-80%                                                                             BF.sub.3                                                                           EDC-80%                                                                             87.5 0.0 32.2                                                                              0.044                                                                             7.1*                                                                              7.05 5.3*                      6   3.0/1                                                                              EDC-80%                                                                             BF.sub. 3                                                                          EDC-80%                                                                             70.0 5.67                                                                              30.0                                                                              1.94                                                                              11.4*                                                                             9.46 5.1*                      7   2.3/1                                                                              EDC-80%                                                                             BF.sub.3                                                                           EDC-80%                                                                             72.5 0.0 28.4                                                                              2.89                                                                              5.2 2.31 8.4                       8   3.0/1                                                                              EDC-80%                                                                             BF.sub.3                                                                           EDC-80%                                                                             85.0 4.45                                                                              31.8                                                                              0.025                                                                             9.7*                                                                              9.68 4.1*                      9   3.0/1                                                                              EDC-80%                                                                             BF.sub.3                                                                           EDC-80%                                                                             85.0 5.57                                                                              31.8                                                                              0.064                                                                             7.1*                                                                              7.04 5.0*                      10  2.5/1                                                                              EDC-80%                                                                             BF.sub.3                                                                           EDC-80%                                                                             85.0 0.00                                                                              31.4                                                                              0.13                                   11  3.0/1                                                                              EDC-80%                                                                             HF   EDC-80%                                                                             85.0 0.22                                                                              33.0                                                                              0.073                                                                             8.32                                                                              8.82 6.7                                      (50% aq.                                                                      sol.)                                                          __________________________________________________________________________     *Analyses run by Infrared  other determinations were by Standard Wet          Method.                                                                       **Dehydrohalogenation reaction conducted at 30° C. and 35-40 mm Hg     instead of 83°-86° C. at 760 mm Hg.                             (1) Theoretical amount of caustic is calculated as an equivalent of           caustic per equivalent of epichlorohydrin added to the glycerine.        

EXAMPLE 4

In the same manner as Example 1, experiments were conducted to show thepreparation of higher molecular weight water-soluble glycidyl ethers ofglycerine and to show the effect of variations in the combined epoxideequivalent weight of the epoxy alkyl halide and the glycidyl ether ofglycerine additive. The results of such experiments are summarized inthe following Table IV:

                                      TABLE IV                                    __________________________________________________________________________                     Equi-      Equivalents                                                    Insol-                                                                            valents                                                                            Equivalents                                                                         of Addi-                                              Additive ubles                                                                             of Addi-                                                                           of Epi-                                                                             tive + Epi-                                                                         Caustic,                                        Employed as                                                                            in  tive/                                                                              chloro-                                                                             chloro-                                                                             % of Insolubles                                                                              %                            Exper-                                                                            a Mixture                                                                              Addi-                                                                             2 moles                                                                            hydrin/                                                                             hydrin/                                                                             Theor-                                                                             in    %   Hydroly-                                                                           %    %                  iment                                                                             with Epi-                                                                              tive,                                                                             of Glyc-                                                                           2 moles of                                                                          1 mole                                                                              etical                                                                             Product,                                                                            Epox-                                                                             zable                                                                              Total                                                                              Total              No. chlorohydrin                                                                           Vol. %                                                                            erine                                                                              Glycerine                                                                           Glycerine                                                                           (1)  Vol. %                                                                              ide Chloride                                                                           Chloride                                                                           OH                 __________________________________________________________________________    1   Expt. 3 of Ex. 1                                                                       0.0 0.288                                                                              3.712 2.0   90.0 0.0   26.8                                                                              0.04 <1.0*                                                                              8.6*               2   Expt. 1 of Ex. 1                                                                       0.0 0.144                                                                              3.856 2.0   85.0 0.5   29.2                                                                              0.086                                                                              1.0* 8.5*               3   Expt. 1 of Ex. 1                                                                       0.0 0.420                                                                              3.580 2.0   87.5 0.0   25.9                                                                              0.172                                                                              <1.0*                                                                              9.9*               4   Expt. 6 of Ex. 2                                                                       0.1 0.144                                                                              5.056 2.6   87.5 0.0   29.9                                                                              0.0413                                                                             7.0* 5.5*               5   Expt. 8 of Ex. 3                                                                       4.45                                                                              0.300                                                                              5.200  2.75 72.5 3.33  27.0                                                                              2.10 8.7* 8.1*               6   Expt. 9 of Ex. 3                                                                       5.57                                                                              0.416                                                                              5.584  04   85.0 7.78  28.2                                                                              0.051                                                                              7.1* 5.0*               7   Expt. 6 of Ex. 1                                                                       4.45                                                                              0.200                                                                              5.000 2.6   72.5 1.11  26.0                                                                              2.20 9.0* 8.4*               8   Expt. 10 of Ex. 3                                                                      0.00                                                                              0.144                                                                              5.056 2.6   72.5 0.22  26.4                                                                              2.48 8.9* 8.3*               9   Expt. 8 of Ex. 4                                                                       0.22                                                                              0.191                                                                              5.009 2.6   72.5 0.89  26.5                                                                              1.80 9.0* 8.2*               10  Expt. 10 of Ex. 3                                                                      0.00                                                                              0.245                                                                              4.955 2.6   87.5 1.11  28.9                                                                              0.18 8.5* 4.7*               11  Expt. 3 of Ex. 3                                                                       0.0 0.338                                                                              4.862 2.6   87.5 0.0   27.4                                                                              0.043                                                                              7.5  7.7                12  "        0.0 0.576                                                                              4.624 2.6   87.5 0.0   24.7                                                                              0.075                                                                              6.6  8.4                13  "        0.0 1.08 4.12  2.6   90.0 0.0   19.6                                                                              0.024                                                                              5.7  9.2                14  "        0.0 1.08 3.12  2.1   90.0 0.0   16.7                                                                              0.16 5.6  13.2               15  D.E.R. 732**                                                                           66.7                                                                              0.156                                                                              5.04 2.6                                                                            87.5  0.8  27.7  0.064                                                                             7.4   5.6                    __________________________________________________________________________     *Analysis run by infrared  other determinations by standard wet method.       **D.E.R. 732 is the diglycidyl ether of a 400 molecular weight                polyoxyalkylene glycol, said diglycidyl ether having an epoxide equivalen     weight of 330.                                                                (1) Theoretical amount of caustic is calculated as an equivalent of           caustic per equivalent of epichlorohydrin added to the glycerine.        

EXAMPLE 5

A reaction vessel was employed which was fitted with a temperatureindicator, a stirrer, a condenser attached to a separating device foraqueous and organic layers and a means for continuously removing aslurry of reactants, products and salts, separating the salt from saidslurry and returning the liquid portion thereof to the reaction vessel.Into such a vessel was charged 92.1 grams (1 mole) of glycerine, 138.0grams of ethylene dichloride and 4.25 grams (0.03 moles) of borontrifluoride etherate. The temperature of the reaction vessel contentswas raised to 55°-60° C. and 229.0 grams (2.477 moles) ofepichlorohydrin containing 17.5 grams (0.122 epoxide equivalents) of theproduct from experiment 2 of Example 2 was added over a period of 1hour. The temperature was allowed to exotherm to 90° C. (reflux) duringthe addition. After digesting for 15 minutes at 90° C., 78.2 grams (1.98moles) of 50% aqueous sodium hydroxide was slowly added at 88° C. As thecaustic was added, the water was continuously removed as an ethylenedichloride-water azeotrope and the ethylene dichloride was returned tothe vessel. Also as the caustic was added, a salt slurry from thereaction vessel was continuously circulated through a filter to removethe salt and the liquid portion thereof was returned to the reactionvessel. After all the caustic had been added, the reaction was continueduntil no more water was collected. The ethylene dichloride containingthe product was then pumped out of the reaction vessel through thefilter and the ethylene dichloride solvent was removed from the productby distilling under reduced pressure. The % yield of recovered productwas 90.2. The product had the following properties.

    ______________________________________                                        % epoxide            27.06                                                    % insolubles         0.0                                                      % total chloride     6.76                                                     % total OH           6.76                                                     % hydrolyzable chloride                                                                            0.02                                                     ______________________________________                                    

EXAMPLE 6

A reaction vessel was employed which was fitted with a temperatureindicator, a stirrer and a condenser attached to a separating device foraqueous and organic layers. Into such a vessel was charged 92.1 grams (1mole) of glycerine, 23 grams of ethylene dichloride and 4.25 grams ofboron trifluoride etherate. The temperature of reaction vessel contentswas raised to 55°-60° C. and 229.0 grams (2.477 moles) ofepichlorohydrin containing 17.5 grams (0.122 epoxide equivalents) of theproduct from experiment 2 of example 2 was added over a period of 1hour. The temperature was allowed to exotherm to 90° C. (reflux) duringthe addition. After digesting for 30 minutes at 90° C., the contentswere cooled to 84° C. and 345 grams of ethylene dichloride were added.The temperature was maintained at 84° C. and 173.5 grams (2.16 moles) of50% aqueous sodium hydroxide was slowly added over a 2-hour period. Asthe NaOH was added, water, produced by the reaction and introduced withthe NaOH, was continuously removed as an ethylene dichloride-waterazeotrope and the ethylene dichloride was separated from the water andreturned to the reaction vessel via the separating device. After all thewater added with the caustic and that produced by the epoxidationreaction had been removed, the contents were digested for 15 minutes at83° C. The salt was then removed from the product-ethylenedichloride-salt slurry by filtration and the product recovered from theproduct-ethylene dichloride filtrate by removing the ethylene-dichlorideby distillation under reduced pressure. A 93.6% yield of product wasrecovered, such product having the following properties:

    ______________________________________                                        % epoxide            27.3                                                     % insolubles         1.95                                                     % hydrolyzable chloride                                                                            0.35                                                     % total chloride     8.03                                                     % total OH           6.59                                                     ______________________________________                                    

EXAMPLE 7

A reaction vessel was employed which was fitted with a temperatureindicator, a stirrer and a condenser attached to a separating device forthe aqueous and organic layers. Into such flask was added glycerine andpolyhydroxyl containing compounds, ethylene dichloride (75 wt. percentbased on solvent, glycerol and polyhydroxyl-containing compound), andBF₃ etherate (0.03 mole per total moles of glycerine andpolyhydroxyl-containing compound). After heating such mixture to 55°-60°C., epichlorohydrin was added over a period of between about 15 minutesand 6 hours while maintaining the 55°-60° C. temperature. After theepichlorohydrin addition was complete, the solution was digested at 60°C. for 30 minutes after which the temperature was increased to 83°C.-86° C. and a quantity of 50 weight percent aqueous NaOH was slowlyadded thereto over a period of from 30 minutes to 8 hours whilemaintaining the temperature. During the NaOH addition, water wascontinuously removed from the reaction vessel as an azeotrope with EDC.The water was separated from the condensed azeotrope and the solventreturned to the reaction vessel. Heating and distillation continued forabout 15 minutes until no more water distilled from the reactionmixture. The reaction mixture was then allowed to cool, the salt wasremoved by filtration, and the product was recovered by flashing the EDCsolvent therefrom.

Analysis of the product was the made for percent epoxide, percenthydrolyzable chloride, percent OH and percent total chloride by standardanalytical methods and percent insolubles was determined by mixing 10gm. (9 ml) of product with sufficient water to produce a total volume of100 ml, shaking the mixture for about 1 minute and centrifuging toremove the water-insolubles therefrom. The volume of such insolubles wasthen calculated as a percent by volume of the original sample.

The following table of experiments (Table V) gives the results obtainedfrom each experiment.

                                      TABLE V                                     __________________________________________________________________________    Compound Mixed with Glycerine                                                                      Moles of Epi-                                                          Quantity                                                                             chlorohydrin/                                                          (wt.% based                                                                          total moles of                                                                         Caustic  %                                                    on total wt.                                                                         glycerine +                                                                            % of %   Hydroly-                                                                           %                                 Experi-       of glycerine                                                                         compound mixed                                                                         Theore-                                                                            Insol-                                                                            zable                                                                              Total                                                                              %  %                         ment No.                                                                           Type     + compound)                                                                          with glycerine                                                                         tical (1)                                                                          ubles                                                                             Chloride                                                                           Chloride                                                                           OH Epoxide                   __________________________________________________________________________    1    polyglycerol                                                                  mw = 388 20     2.6      87.5 0.0 <0.005                                                                             7.66 5.9                                                                              29.0                      2    polyglycerol                                                                  mw = 388 30     2.6      87.5 0.0 0.026                                                                              8.4  6.4                                                                              28.0                      3    polyglycerol                                                                  mw = 388 50     2.6      87.5 0.0 0.022                                                                              6.6  10.9                                                                             24.0                      4    polyglycerol                                                                  mw = 388 50     2.0      87.5 0.0 0.032                                                                              6.9  18.2                                                                             19.8                      5    polyglycerol                                                                  mw = 388 70     2.0      87.5 2.2 0.05 9.2  18.3                                                                             14.8                      6    polyoxypropylene                                                              glycol, mw = 400                                                                       33.1   1.6      90.0 0.0 0.03 3.5  11.6                                                                             22.6                      7    polyoxypropylene                                                              glycol, mw = 400                                                                       56.8   1.6      90.0 0.0 0.024                                                                              2.46 9.86                                                                             17.8                      __________________________________________________________________________

We claim:
 1. Water-soluble epoxy resins which are the dehydrohalogenatedLewis Acid catalyzed reaction product of glycerine with a mixturecontaining(a) from about 0.05 to about 0.65 epoxide equivalents per moleof glycerine of a glycidyl ether of a compound having more than onealiphatic hydroxyl group selected from the group consisting of aglycidyl ether of glycerine epoxyalkyl halide adduct, a diglycidyl etherof a 200-600 molecular weight polyoxyalkylene glycol or mixtures thereofand (b) from about 1.35 to about 2.95 epoxide equivalents per mole ofglycerine of an epoxy alkyl halide having the epoxy group α, β to thehalogen wherein the sum of a and b is in the range from about 2.0 toabout 2.6 or when the Lewis Acid catalyst is SnCl₄ or HF from about 2.0to about 3 epoxide equivalents per mole of glycerine;wherein said watersoluble epoxy resin contains from about 1.5% to about 8% organicchloride by weight, an epoxide content of from about 26% to about 33% byweight, and less than about 2% by volume of water-insoluble glycidylether constituents.
 2. The water-soluble epoxy resin product of claim 1wherein the epoxyalkyl halide is epichlorohydrin.
 3. The water-solubleepoxy resins of claims 1 or 2 wherein component (a) is a glycidyl etherof glycerine epoxyalkyl halide adduct.
 4. The water-soluble epoxy resinof claim 3 wherein the percent of insolubles contained in (a) is lessthan about 10 percent.
 5. A process for the preparation of awater-soluble epoxy resin wherein in said process(1) glycerine isreacted in a vessel with a mixture comprising (a) from about 0.05 toabout 0.65 epoxide equivalents per mole of glycerine of a glycidyl etherof a compound having more than one aliphatic hydroxyl group selectedfrom the group consisting of a glycidyl ether of glycerine epoxyalkylhalide adduct, a diglycidyl ether of a 200-600 molecular weightpolyoxyalkylene glycol or mixtures thereof and (b) from about 1.35 toabout 2.95 epoxide equivalents per mole of glycerine of an epoxyalkylhalide having the epoxy group α, β to the halogen in the presence of acatalyzing amount of a Lewis Acid catalyst wherein the total quantity of(a) and (b) per mole of glycerine is from about 2.0 to about 3.0 whenthe Lewis Acid is SnCl₄ or HF otherwise it is from about 2.0 to about2.6 and the reaction is conducted in an organic solvent in which theglycerine is at least partially soluble and in which the chlorohydrinether reaction product will form a single phase; (2)dehydrohalogenating, at a temperature below about 110° C., thechlorohydrin ether reaction product with an alkaline-acting material inthe presence of at least 50 weight percent (based upon the combinedweights of glycerine and total quantity of solvent) of an organic liquidwhich is a solvent for the glycidyl ether product to produce a glycidylether of glycerine containing less than about 2 percent by volume ofwater-insoluble glycidyl ether constituents; (3) separating the waterresulting from the dehydrohalogenation reaction and caustic addition byazeotropic distillation and (4) separating the salt from the resultingsolution.
 6. The process of claim 5 wherein the epoxy alkyl halide isepichlorohydrin.
 7. The process of claim 6 wherein the alkaline actingmaterial is NaOH and the organic solvent employed in thedehydrohalogenation step is ethylene dichloride.
 8. The process of claim6 wherein the organic solvent in both steps (1) and (2) is ethylenedichloride.
 9. The process of claim 6 wherein the reaction of glycerineand the mixture of a glycidyl ether of glycerine epoxyalkyl halideadduct and/or diglycidyl ether of a 200-600 molecular weightpolyoxyalkylene glycol and epichlorohydrin is conducted at a temperatureof between about 0° C. and the reflux temperature of the solventemployed.
 10. The process of claim 6 wherein the salt formed during thedehydrohalogenation reaction is removed continuously by passing aportion of the salts containing reaction mixture through a filter andreturning the filtrate to the reaction vessel.
 11. The process of claims5, 6, 7, 8, 9 or 10 wherein component (a) is a glycidyl ether ofglycerine epoxyalkyl halide adduct containing less than about 10 percentinsolubles by weight.